Polyurethane/urea compositions

ABSTRACT

A valve in the form of a medical device, article, or implant that is composed wholly or partly of a biomaterial, the biomaterial comprising a polyurethane or polyurethane urea elastomeric composition having a plurality of soft segments and hard segments, such that the plurality of soft segments are each derived from at least one block copolymer segment of Formula 1 and optionally an additional polyol or polyamine. The valve may include a plurality of 
                         
valve leaflets and a support structure with one or more of the valve leaflets being composed wholly or partly of the biomaterial.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent application Ser. No. 15/150,737, filed May 10, 2016, now U.S. Pat. No. 10,266,657, which claims priority from Australian Provisional Patent Application No. 2015904428, filed on 29 Oct. 2015, the entire contents of each of which are incorporated herein by reference in their entireties.

FIELD

The present disclosure relates to soft block copolymer segments for a thermoplastic polyurethane or polyurethaneurea elastomer composition and their reaction products with divalent compounds, such as diisocyanates, chain extenders and optional additional polyols or polyamines. Also disclosed are methods for the preparation of the soft block copolymer segments and reaction products, and the use of these components in the manufacture of materials such as biomaterials for devices, articles or implants.

BACKGROUND

The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.

Previously, polyurethanes based on two or more macrodiols which are chemically different have been reported. This has been achieved by using a mixture or a blend of the macrodiols for making the polyurethane, and employing either a one-step or a two-step polymerisation procedure. This approach has a number of disadvantages including: in most cases, if the macrodiols are not miscible, the resulting polyurethane is compositionally heterogeneous; only a limited number of macrodiol combinations can be used to make polyurethanes with good mechanical properties, and the segments from each of the macrodiols are randomly distributed within the polyurethane chain (often resulting in polyurethanes with poor mechanical properties); and the incorporation of higher molecular weight macrodiols or macrodiamines are limited to polyols such as polyether, polyester or polycarbonates.

There is a need for identifying alternative block copolymers for use in polyurethane or polyurethaneurea elastomer compositions for preparing various polymer products with a broad range of mechanical properties. The alternative block copolymers may address one or more disadvantages of previous approaches.

Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present disclosure as it existed before the priority date of each claim of this application.

SUMMARY

The present disclosure relates to macrodiols and macrodiamines which are chemically linked (linked-macrodiols or macrodiamines) to contain one or more chemically distinct moieties within a polymeric backbone. The said macrodiols and macrodiamines are useful in formulating polyurethanes/ureas for biomedical and non-biomedical applications.

In a first aspect, there is provided a block copolymer segment of Formula 1 for a thermoplastic polyurethane or polyurethaneurea elastomer composition:

wherein

A¹ is an endcapping group;

A² is hydrogen or an endcapping group;

each Y¹ and Y² are independently selected from a polysiloxane macrodiol, polysiloxane macrodiamine, polyether macrodiol, polycarbonate macrodiol, polyester macrodiol, and a polyhydrocarbon macrodiol;

each L¹ and L² is a divalent linking group independently selected from urethane, urea carbonate, amide, ester, and phosphonate;

n is an integer of 1 to 5;

t is an integer of 0 to 5; and

Q is selected from a moiety according to:

-   -   wherein     -   R¹, R², R³, and R⁴, are each independently selected from         hydrogen and an optionally substituted straight chain, branched         or cyclic, saturated and unsaturated hydrocarbon radical;     -   R⁵ and R⁶ are each independently selected from a straight chain,         branched or cyclic, saturated and unsaturated hydrocarbon         radical optionally interrupted with one or more heteroatoms         independently selected from O, N and S;     -   m is an integer of 1 to 50;     -   X is a group selected from OC(O)O, C(O)O and O;     -   q is an integer of 1 to 50; and r is an integer of 2 to 50.

In a second aspect, there is provided a thermoplastic polyurethane or polyurethaneurea elastomer composition comprising a plurality of soft segments and hard segments, wherein the plurality of soft segments are each derived from at least one block copolymer segment of Formula 1 according to the first aspect above, or any embodiments thereof described herein, and optionally an additional polyol or polyamine.

In a third aspect, there is provided a thermoplastic polyurethane or polyurethaneurea elastomer composition comprising a reaction product of:

-   -   i. at least one block copolymer segment of Formula 1 according         to the first aspect above, or any embodiments thereof described         herein;     -   ii. a diisocyanate;     -   iii. one or more chain extenders; and     -   iv. optionally an additional polyol or polyamine.

In a fourth aspect, there is provided a material comprising a thermoplastic polyurethane or polyurethaneurea elastomeric composition according to the above second or third aspect, or any embodiments thereof described herein.

In a fifth aspect, there is provided a device or article which is composed wholly or partly of the polyurethane or polyurethaneurea elastomeric composition according to the above second or third aspect, or any embodiments thereof described herein.

In a sixth aspect, there is provided a medical device, article or implant which is composed wholly or partly of the polyurethane or polyurethaneurea elastomeric composition according to the above second or third aspect, or any embodiments thereof described herein.

In a seventh aspect, there is provided process for preparing the block copolymer segment of Formula 1 according to the first aspect above, or any embodiments thereof described herein, whereby the process comprises the step of combining:

-   -   i. at least one macrodiol; or     -   ii. at least one macrodiamine; or     -   iii. a mixture of at least one macrodiol and at least one         macrodiamine, with a divalent linking compound.

In an eighth aspect, there is provided a process for preparing a thermoplastic polyurethane or polyurethaneurea elastomer comprising the silicon based block copolymer segment of Formula 1 according to the first aspect above, or any embodiments thereof described herein, whereby the process comprises the steps of:

-   -   i. providing a block copolymer segment of Formula 1 according to         the first aspect above, or any embodiments thereof described         herein, or preparing a block copolymer segment of Formula 1         using the process according to the seventh aspect, or any         embodiments thereof described herein;     -   ii. optionally reacting the composition of step i. with a         divalent compound and: at least one macrodiol; at least one         macrodiamine; or a mixture of at least one macrodiol and at         least one macrodiamine; and     -   iii. reacting the block copolymer segment of step i. or step ii.         with a chain extender or a mixture of chain extenders to form         the polyurethane or polyurethaneurea elastomer

Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for the purpose of illustration only and are not intended to limit the scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

FIG. 1 is a perspective view of an example embodiment of a prosthetic heart valve incorporating polymers disclosed herein.

DETAILED DESCRIPTION

The present disclosure describes the following various non-limiting embodiments, which relate to investigations undertaken to identify alternative block copolymer segments for use in polyurethane/urea compositions and polymer products thereof. It was surprisingly found that the block copolymer segments disclosed herein can provide a number of advantages including enhanced soft segment properties in polyurethane/urea thermoplastic polymers. Enhanced soft segment properties include an improved miscibility with hard segments and increased inter molecular hydrogen bonding.

According to at least some embodiments described herein, the block copolymers, polyurethane/urea compositions and polymer products thereof can provide advantages including:

-   -   allowing a wide range of macrodiols, including those that are         not miscible with each other, to be linked to produce a raft of         different linked macrodiols which act as “macro-monomers”;     -   the formulation of polyurethanes with low modulus, high         elasticity and high tear strength for use in cardio vascular         medical implants;     -   by utilising certain linker molecules, the synthesis of the         linked-macrodiol can be prepared prior to the         polyurethane/polyurethaneurea synthesis, without involving any         purification steps; and     -   the ability to increase the molecular weight of a         “macro-monomer” by linking two or more macrodiols or diamine         molecules, allows for the formulation of materials with a wide         range of mechanical properties, via the variation in the         relative proportions of ‘soft’ segments (for example a segment         derived from the macrodiol or macrodiamine), and hard segments         (for example a segment derived from the diisocyanate and an         optional chain extender).         Terms

With regards to the definitions provided herein, unless stated otherwise, or implicit from context, the defined terms and phrases include the provided meanings. Unless explicitly stated otherwise, or apparent from context, the terms and phrases below do not exclude the meaning that the term or phrase has acquired by a person skilled in the relevant art. The definitions are provided to aid in describing particular embodiments, and are not intended to limit the claimed invention, because the scope of the invention is limited only by the claims. Furthermore, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.

Herein, the term “polyurethane” relates to a polymer chain that comprises urethane (carbamate, —NH—COO—) links which connect monomer or “macro-monomer” units. Polyurethanes can be produced via the reaction of molecules containing a minimum of two isocyanate functional groups with other molecules which contain at least two alcohol (hydroxyl) groups.

Herein, the term “polyureas” relates to a polymer chain that comprises urea links (—NH—CO—NH—) which connect monomer or “macro-monomer” units. Polyureas can be produced via the reaction of molecules containing a minimum of two isocyanate groups with other molecules which contain at least two amine groups.

Herein, the term “polyurethaneurea” relates to a polymer chain that comprises both urethane and urea linking groups.

Herein, the term “macrodiol” refers to a polymeric material comprising two hydroxyl groups. For example, a block copolymer segment of Formula 1 with two hydroxyl groups.

Herein, the term “macrodiamine” refers to a polymeric material comprising two amine groups. For example, a block copolymer segment of Formula 1 with two amine groups.

Herein, the term “polyhydrocarbon macrodiol” refers to a polymeric material with a polymer backbone consisting entirely of hydrogen and carbon, and two hydroxyl groups. Examples include, but are not limited to: poly(isobutylene)diol, poly(butadiene)diol and hydrogenated poly(butadiene diol).

The term “macro-monomer” refers to a polymeric substance that possesses at least one polymerisable group, for example a hydroxyl group, which is capable of reacting with another compound, for example a diisocyanate.

Throughout the present specification, various aspects and components of the invention can be presented in a range format. The range format is included for convenience and should not be interpreted as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range, unless specifically indicated. For example, description of a range such as from 1 to 5 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 5, from 3 to 5 etc., as well as individual and partial (except where integers are required), numbers within the recited range, for example, 1, 2, 3, 4, 5, 5.5 and 6. This applies regardless of the breadth of the disclosed range. Where specific values are required, these will be indicated in the specification.

Herein, the term “hydrocarbon radical” refers to an optionally substituted straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical. The hydrocarbon radical (for example for substituents R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and/or R¹²) includes optionally substituted alkyl, alkenyl, alkynyl, aryl or heterocyclyl radicals.

The term “alkyl” denotes straight chain, branched or mono- or poly-cyclic alkyl, for example C₁₋₁₈alkyls or C₃₋₈cycloalkyls. “C₁₋₁₈ alkyls” and “C₃₋₈ cycloalkyls” refer to alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 8 carbon atoms.

As understood by a person skilled in the art, the term “C₁₋₁₈ alkyls” means alkyl groups with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18 carbon atoms or a range comprising any of two of those integers and including 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-12, 2-13, 2-14, 2-15, 2-16, 2-17, 2-18, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 3-13, 3-14, 3-15, 3-16, 3-17, 3-18, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 4-12, 4-13, 4-14, 4-15, 4-16, 4-17, 4-18, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 5-12, 5-13, 5-14, 5-15, 5-16, 5-17, 5-18, 6-7, 6-8, 6-9, 6-10, 6-11, 6-12, 6-13, 6-14, 6-15, 6-16, 6-17, 6-18, 7-8, 7-9, 7-10, 7-11, 7-12, 7-13, 7-14, 7-15, 7-16, 7-17, 7-18, 8-9, 8-10, 8-11, 8-12, 8-13, 8-14, 8-15, 8-16, 8-17, 8-18, 9-10, 9-11, 9-12, 9-13, 9-14, 9-15, 9-16, 9-17, 9-18, 10-11, 10-12, 10-13, 10-14, 10-15, 10-16, 10-17, 10-18, 11-12, 11-13, 11-14, 11-15, 11-16, 11-17, 11-18, 12-13, 12-14, 12-15, 12-16, 12-17, 12-18, 13-14, 13-15, 13-16, 13-17, 13-18, 14-15, 14-16, 14-17, 14-18, 15-16, 15-17, 15-18, 16-17, 16-18, or 17-18 carbon atoms. Examples of straight chain and branched alkyl groups include optionally substituted: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, amyl, isoamyl, sec-amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, hexyl, 4-methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dinethylbutyl, 1,2,2-trimethylpropyl, or 1,1,2-trimethylpropyl, heptyl, 5-methylhexyl, 1-methylhexyl, 2,2-dimethylpentyl, 3,3-dimethylpentyl, 4,4-dimethylpentyl, 1,2-dimethylpentyl, 1,3-dimethylpentyl, 1,4-dimethylpentyl, 1,2,3-trimethylbutyl, 1,1,2-trimethylbutyl, 1,1,3-trimethylbutyl, octyl, 6-methylheptyl, 1-methyheptyl and 1,1,3,3-tetramethylbutyl groups, nonyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-methyloctyl, 1-, 2-, 3-, 4- or 5-ethylheptyl, 1-, 2- or 3-propylhexyl, decyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- and 8-methylnonyl, 1-, 2-, 3-, 4-, 5- or 6-ethyloctyl, 1-, 2-, 3-, or 4-propylheptyl, undecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-methyldecyl, 1-, 2-, 3-, 4-, 5-, 6- or 7-ethylnonyl. 1-, 2-, 3-, 4- or 5-propyloctyl, 1-, 2- or 3-butylheptyl, 1-pentylhexyl, dodecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-methylundecyl, 1-, 2-, 3-, 4-, 5-, 6-, 7- or 8-ethyldecyl, 1-, 2-, 3-, 4-, 5- or 6-propylnonyl, 1-, 2-, 3- or 4-butyloctyl, 1,2-pentylheptyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.

As understood by a person skilled in the art, the term “C₃₋₈ cycloalkyls” means cycloalkyl groups with 3, 4, 5, 6, 7 or 8 carbon atoms or a range comprising any of two of those integers and including 3-4, 3-5, 3-6, 3-7, 3-8, 4-5, 4-6, 4-7, 4-8, 5-6, 5-7, 5-8, 6-7, 6-8 or 7-8 carbon atoms. Examples of cyclic alkyl groups include optionally substituted: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl groups.

The term “alkenyl” relates to groups formed from straight chain, branched or mono- or poly-cyclic alkenes including ethylenically mono- or poly-unsaturated alkyl or cycloalkyl groups as defined above, for example C₂₋₁₈ alkenyls or C₃₋₈ cycloalkenyls. “C₂₋₁₈ alkenyls” or “C₃₋₈ cycloalkenyls” refer to alkenyl or cycloalkenyl groups having 2 to 18 carbon atoms or 3 to 8 carbon atoms, respectively.

As understood by a person skilled in the art, the term “C₂₋₈ alkenyls” means alkenyl groups with 2, 3, 4, 5, 6, 7 or 8 carbon atoms or a range comprising any of two of those integers and including 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 2-12, 2-13, 2-14, 2-15, 2-16, 2-17, 2-18, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 3-12, 3-13, 3-14, 3-15, 3-16, 3-17, 3-18, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 4-12, 4-13, 4-14, 4-15, 4-16, 4-17, 4-18, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 5-12, 5-13, 5-14, 5-15, 5-16, 5-17, 5-18, 6-7, 6-8, 6-9, 6-10, 6-11, 6-12, 6-13, 6-14, 6-15, 6-16, 6-17, 6-18, 7-8, 7-9, 7-10, 7-11, 7-12, 7-13, 7-14, 7-15, 7-16, 7-17, 7-18, 8-9, 8-10, 8-11, 8-12, 8-13, 8-14, 8-15, 8-16, 8-17, 8-18, 9-10, 9-11, 9-12, 9-13, 9-14, 9-15, 9-16, 9-17, 9-18, 10-11, 10-12, 10-13, 10-14, 10-15, 10-16, 10-17, 10-18, 11-12, 11-13, 11-14, 11-15, 11-16, 11-17, 11-18, 12-13, 12-14, 12-15, 12-16, 12-17, 12-18, 13-14, 13-15, 13-16, 13-17, 13-18, 14-15, 14-16, 14-17, 14-18, 15-16, 15-17, 15-18, 16-17, 16-18, or 17-18 carbon atoms. As understood by a person skilled in the art, the term “C₃₋₈ cycloalkenyls” means cycloalkenyl groups with 3, 4, 5, 6, 7 or 8 carbon atoms or a range comprising any of two of those integers and including 3-4, 3-5, 3-6, 3-7, 3-8, 4-5, 4-6, 4-7, 4-8, 5-6, 5-7, 5-8, 6-7, 6-8 or 7-8 carbon atoms. Examples of alkenyls and cycloalkenyls include optionally substituted: vinyl, allyl, 1-methylvinyl, butenyl, iso-butenyl, 3-methyl-2-butenyl, 1-pentenyl, cyclopentenyl, 1-methyl-cyclopentenyl, 1-hexenyl, 3-hexenyl, cyclohexenyl, 1-heptenyl, 3-heptenyl, 1-octenyl, cyclooctenyl, 1,3-butadienyl, 1,4-pentadienyl, 1,3-cyclopentadienyl, 1,3-hexadienyl, 1,4-hexadienyl, 1,3-cyclohexadienyl, 1,4-cyclohexadienyl, 1,3-cycloheptadienyl, 1,3,5-cycloheptatrienyl and 1,3,5,7-cyclooctatetraenyl groups.

The term “alkynyl” denotes groups formed from straight chain, branched, or mono- or poly-cyclic alkynes, for example C₂₋₁₈alkynyls or C₃₋₈cycloalkynyls. Examples of alkynyl include optionally substituted: ethynyl, 1-propynyl, 1 and 2-butynyl, 2-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl groups, 10-undecynyl, 4-ethyl-1-octyn-3-yl, 7-dodecynyl, 9-dodecynyl, 10-dodecynyl, 3-methyl-2-dodecyn-3-yl, 2-tridecynyl, 11-tridecynyl, 3-tetradecynyl, 7-hexadecynyl and 3-octadecynyl.

The term “aryl” denotes single, polynuclear, conjugated and fused residues of aromatic hydrocarbons. Examples of aryl include optionally substituted: phenyl, biphenyl, terphenyl, quaterphenyl, phenoxyphenyl, naphthyl, tetrahydronaphthyl, anthracenyl, dihydroanthracenyl, benzanthracenyl, dibenzanthracenyl and phenanthrenyl groups.

The term “heterocyclyl” denotes mono- or poly-cyclic heterocyclyl groups containing at least one heteroatom selected from nitrogen, sulphur and oxygen. Suitable heterocyclyl groups include optionally substituted: N-containing heterocyclic groups, such as, unsaturated 3 to 6 membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, for example, pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl or tetrazolyl; saturated 3 to 6-membered heteromonocyclic groups containing 1 to 4 nitrogen atoms, such as pyrrolidinyl, imidazolidinyl, piperidino or piperazinyl; unsaturated condensed heterocyclic groups containing 1 to 5 nitrogen atoms, such as, indolyl, isoindolyl, indolizinyl, benzimidazolyl, quinolyl, isoquinolyl, indazolyl, benzotriazolyl or tetrazolopyridazinyl; unsaturated 3 to 6-membered heteromonocyclic group containing an oxygen atom, such as, pyranyl or furyl; unsaturated 3 to 6-membered hetermonocyclic group containing 1 to 2 sulphur atoms, such as, thienyl; unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, oxazolyl, isoazolyl or oxadiazolyl; saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, morpholinyl; unsaturated condensed heterocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, such as, benzoxazolyl or benzoxadiazolyl; unsaturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as thiazolyl or thiadiazolyl; saturated 3 to 6-membered heteromonocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as, thiadiazolyl; and unsaturated condensed heterocyclic group containing 1 to 2 sulphur atoms and 1 to 3 nitrogen atoms, such as benzothiazolyl or benzothiadiazolyl groups.

Herein, “optionally substituted” means that a group may or may not be further substituted with one or more groups selected from oxygen, nitrogen, sulphur, alkyl, alkenyl, alkynyl, aryl, halo, haloalkyl, haloalkenyl, haloalkynyl, haloaryl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, aryloxy, carboxy, benzyloxy, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloaryloxy, nitro, nitroalkyl, nitroalkenyl, nitroalkynyl, nitroaryl, nitroheterocyclyl, azido, amino, alkylamino, alkenylamino, alkynylamino, arylamino, benzylamino, acyl, alkenylacyl, alkynylacyl, arylacyl, acylamino, acyloxy, aldehydo, alkylsulphonyl, arylsulphonyl, alkyl sulphonylamino, aryl sulphonylamino, alkylsulphonyloxy, arylsulphonyloxy, heterocyclyl, heterocycloxy, heterocyclylamino, haloheterocyclyl, alkylsulphenyl, arylsulphenyl, carboalkoxy, carboaryloxy, mercapto, alkylthio, arylthio, acylthio and the like. It will be appreciated that the term “optionally substituted” may also be referred to as “substituted or unsubstituted”.

Block Copolymer Segments

Disclosed herein are block copolymer segments of Formula 1 for a thermoplastic polyurethane or polyurethaneurea elastomer composition:

wherein

A¹ is an endcapping group;

A² is hydrogen or an endcapping group;

each Y¹ and Y² are independently selected from a polysiloxane macrodiol, polysiloxane macrodiamine, polyether macrodiol, polycarbonate macrodiol, polyester macrodiol, and a polyhydrocarbon macrodiol;

each L¹ and L² is a divalent linking group independently selected from urethane, urea carbonate, amide, ester, and phosphonate;

n is an integer of 1 to 5;

t is an integer of 0 to 5; and

Q is selected from a moiety of Formula A or Formula B:

wherein

R¹, R², R³, and R⁴, are each independently selected from hydrogen and an optionally substituted straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical;

R⁵ and R⁶ are each independently selected from a straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical optionally interrupted with one or more heteroatoms independently selected from O, N and S;

m is an integer of 1 to 50;

X is a group selected from OC(O)O, C(O)O and O; and

q is an integer of 1 to 50; and r is an integer of 2 to 50.

The block copolymer segment may be a block copolymer segment of Formula 1A:

wherein each A¹, A², Y¹, L¹, L², Y², R¹, R², R³, R⁴, R⁵, R⁶, m, n and t, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1A(i):

wherein each A¹, A², L², Y², R¹, R², R³, R⁴, R⁵, R⁶, m and n, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1A(i)(a):

wherein each A¹, A², L², R¹, R², R³, R⁴, R⁵, R⁶, X, m, q and r, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1A(i)(b):

wherein each A¹, A², L², R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², m, n and u, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1A(ii):

wherein each A¹, A², L¹, L², R¹, R², R³, R⁴, R⁵, R⁶, X, m, q, r and t, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1B:

wherein each A¹, A², Y¹, L¹, L², Y², X, n, r, t, and q, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1B(i):

wherein each A¹, A², L², Y², X, q, r and n, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1B(i)(a):

wherein

n is an integer from 1 to 5;

A¹ is an endcapping group;

A² is hydrogen or an endcapping group;

X and X¹ are each independently selected from OC(O)O, C(O)O and O;

q and v are each independently selected from an integer of 1 to 50 (for example 5 to 20); and

r and w are each independently selected from an integer of 2 to 50.

The block copolymer segment may be a block copolymer segment of Formula 1B(i)(b):

wherein each A¹, A², q, X, and r, are as defined in claim 1, and L², n, R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and u, are as defined herein.

The block copolymer segment may be a block copolymer segment of Formula 1B(ii):

wherein each A¹, A², L¹, L², X, n, q, r and t, are as defined in claim 1, and each R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹² and u, are as defined herein.

Substituent Q

Substituent Q may be selected from a moiety of Formula A or Formula B as described herein.

Substituent Q may be selected from a moiety of Formula A:

-   -   wherein     -   R¹, R², R³, and R⁴, are each independently selected from         hydrogen and an optionally substituted straight chain, branched         or cyclic, saturated and unsaturated hydrocarbon radical;     -   R⁵ and R⁶ are each independently selected from a straight chain,         branched or cyclic, saturated and unsaturated hydrocarbon         radical optionally interrupted with one or more heteroatoms         independently selected from O, N and S; and     -   m is an integer of 1 to 50.

Substituent Q may be selected from a moiety of Formula B:

-   -   wherein     -   X is a group selected from OC(O)O, C(O)O and O;     -   q is an integer of 1 to 50; and     -   r is an integer of 2 to 50.

In one embodiment substituent Q is a moiety of Formula A. Q may be α,ω bis-(6-hydroxyethoxypropyl)polydimethylsiloxane. In another embodiment substituent Q is a moiety of Formula B.

Substituent A¹

Herein, substituent A¹ is an “endcapping group” and includes reactive functional groups or groups containing reactive functional groups. Examples of suitable reactive functional groups for substituent A¹ include: hydroxyl groups, carboxylic acids, aldehydes, ketones, esters, acid halides, acid anhydrides, amine groups, imine groups, thio groups, thioesters, sulphonic acids and epoxides.

A¹ may be selected from hydroxyl or amine. In one embodiment, A¹ is a hydroxyl group. In another embodiment, A¹ is an amine group.

Substituent A²

Herein substituent A² is hydrogen or an “endcapping group” and includes reactive functional groups or groups containing reactive functional groups. Examples of suitable reactive functional groups for substituent A² include: hydroxyl groups, carboxylic acids, aldehydes, ketones, esters, acid halides, acid anhydrides, amine groups, imine groups, thio groups, thioesters, sulphonic acids and epoxides.

A² may be selected from hydrogen, hydroxyl or amine. In one embodiment A² is hydrogen. In another embodiment A² is a hydroxyl group. In another embodiment A² is an amine group.

Substituents Y¹ and Y²

Herein each individual substituent Y¹ and Y² are independently selected from a polysiloxane macrodiol, polysiloxane macrodiamine, polyether macrodiol, polycarbonate macrodiol, polyester macrodiol, and a polyhydrocarbon macrodiol.

At least one of Y¹ and Y² may be a polysiloxane macrodiol. Y¹ may be a polysiloxane macrodiol. Y² may be a polysiloxane macrodiol.

Examples of polysiloxane macrodiols include, but are not limited to: polydimethylsiloxane diols, such as α,ω bis-(6-hydroxyethoxypropyl)polydimethylsiloxane, α,ω bis-(4-hydroxybutyl)polydimethylsiloxane and α,ω bis-(3-hydroxypropyl)polydimethylsiloxane.

In one embodiment at least one of Y¹ and Y² is a polydimethylsiloxane diol. In another embodiment both of Y¹ and Y² are polydimethylsiloxane diols. In another embodiment at least one of Y¹ and Y² is α,ω bis-(6-hydroxyethoxypropyl)polydimethylsiloxane. In another embodiment both of Y¹ and Y² are α,ω bis-(6-hydroxyethoxypropyl)polydimethylsiloxane.

At least one of Y¹ and Y² may be a polysiloxane macrodiamine. Y¹ may be a polysiloxane macrodiamine. Y² may be a polysiloxane macrodiamine.

Examples of polysiloxane macrodiamines include, but are not limited to: α,ω bis-(aminomethyl)polydimethylsiloxane, α,ω bis-(2-aminoethyl)polydimethylsiloxane, p, w bis-(3-aminopropyl)polydimethylsiloxane, α,ω bis-(4-aminobutyl)polydimethylsiloxane, α,ω bis-(5-aminopentyl)polydimethylsiloxane and the like.

At least one of Y¹ and Y² may be a polyether macrodiol. Y¹ may be a polyether macrodiol. Y² may be a polyether macrodiol.

Examples of polyether macrodiols include, but are not limited to: poly(ethylene oxide), poly(propylene oxide), poly(butylene oxide), poly(pentylene oxide), poly(hexamethylene oxide) (PHMO), poly(heptamethylene oxide), poly(octamethylene oxide) (POMO) and poly(decamethylene oxide) (PDMO).

In one embodiment at least one of Y¹ and Y² is poly(hexamethylene oxide) (PHMO).

In one embodiment both of Y¹ and Y² are poly(hexamethylene oxide) (PHMO).

At least one of Y¹ and Y² may be a polycarbonate macrodiol. Y¹ may be a polycarbonate macrodiol. Y² may be a polycarbonate macrodiol.

Examples of polycarbonate macrodiols include, but are not limited to: poly(propylene carbonate), poly(hexamethylene carbonate) and polycarbonate and copolycarbonate macrodiols can be prepared by using an ester interchange reaction as described in P. A. Gunatillake et al., Journal of Applied Polymer Science, 69(8) 1621-1633, (1998), for example by reacting a carbonate such as ethylene carbonate with a diol. Appropriate diols include, but are not limited to: 1,6-hexanediol, 1,10-decanediol, 2,2-diethyl-1,3-propanediol, 1,4-cyclohexanedimethanol and bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane.

At least one of Y¹ and Y² may be a polyester macrodiol. Y¹ may be a polyester macrodiol. Y² may be a polyester macrodiol.

Examples of polyester macrodiols include, but are not limited to: poly(caprolactone) diol, poly(tetramethyleneadipate) diol, poly(D,L-lactide) and, poly(glycolide).

At least one of Y¹ and Y² may be a polyhydrocarbon macrodiol. Y¹ may be a polyhydrocarbon macrodiol. Y² may be a polyhydrocarbon macrodiol.

Examples of polyhydrocarbon macrodiols include polymeric aliphatic α,ω-diols. Specific examples of polyhydrocarbon macrodiols include, but are not limited to: poly(isobutylene)diol and poly(butadiene)diols, such as hydrogenated poly(butadiene)diols (including fully hydrogenated poly(butadiene)diols).

In one embodiment, Y¹ and Y² are each independently selected from a moiety of Formula A′ or Formula B′:

wherein

R⁷, R⁸, R⁹, and R¹⁰, are each independently selected from hydrogen and an optionally substituted straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical; and

R¹ and R¹² are each independently selected from a straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical optionally interrupted with one or more heteroatoms independently selected from O, N and S; and

u is an integer of 1 to 50; or

wherein

X¹ is a group selected from OC(O)O, C(O)O and O;

v is an integer of 1 to 50, for example an integer of 5 to 20; and

w is an integer of 2 to 50.

In one embodiment at least one of Y¹ and Y² is a moiety of Formula A′.

In one embodiment at least one of Y¹ and Y² is a moiety of Formula B′.

In another embodiment substituents Y¹ and Y² are the same.

In yet another embodiment substituents Y¹ and Y² are different. It will be appreciated that Y¹ and Y² may be selected from different groups within same individual Formula A′. Similarly, it will also be appreciated that Y¹ and Y² may be selected from different groups within same individual Formula B′.

Substituents L¹ and L²

Herein substituents L¹ and L² are divalent linking groups independently selected from urethane, urea carbonate, amide, ester, and phosphonate linking groups.

At least one of L¹ or L² may be a urethane linking group. L¹ may be a urethane linking group. L² may be a urethane linking group.

Urethane linking groups can be produced by reacting hydroxyl containing compounds, such as a macrodiol, with a diisocyanate. Examples of appropriate diisocyanates include aliphatic, cyclic or aromatic diisocyanates such as, for example: 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, 1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI) trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) or its isomers (for example 2,6-toluene diisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylene diisocyanate (m-TMXDI), 1,6-diisocyanatohexane (DICH), 1,3-bis(1-isocyanato-1-methylethyl)benzene, or 1,5-diisocyanatonaphthalene (NDI).

In one embodiment, L¹ or L² may be independently a linking group of Formula E:

wherein R^(a) is selected from:

-   -   an optionally substituted straight chain, branched or cyclic,         saturated or unsaturated hydrocarbon radical (including         optionally substituted alkyl, alkenyl, alkynyl, aryl or         heterocyclyl radicals).

For example, L¹ or L² may be selected from:

At least one of L¹ or L² may be a urea linking group. L¹ may be a urea linking group. L² may be a urea linking group.

Urea linking groups can be produced by reacting amine containing compounds, such as a macrodiamine, with a diisocyanate. Examples of appropriate diisocyanates include aliphatic, cyclic or aromatic diisocyanates such as, for example: 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, 1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI) trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) or its isomers (for example 2,6-toluene diisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylene diisocyanate (m-TMXDI), or 1,5-diisocyanatonaphthalene (NDI).

In one embodiment, L¹ or L² may be independently a linking group of Formula F:

wherein R^(b) is selected from:

-   -   an optionally substituted straight chain, branched or cyclic,         saturated or unsaturated hydrocarbon radical (including         optionally substituted alkyl, alkenyl, alkynyl, aryl or         heterocyclyl radicals).

For example, L¹ or L² may be selected from:

At least one of L¹ or L² may be a carbonate linking group. L¹ may be a carbonate linking group. L² may be a carbonate linking group.

In one embodiment, L¹ or L² may be independently a linking group of Formula G:

wherein R^(c) is selected from:

-   -   an optionally substituted straight chain, branched or cyclic,         saturated or unsaturated hydrocarbon radical (including         optionally substituted alkyl, alkenyl, alkynyl, aryl or         heterocyclyl radicals).

At least one of L¹ or L² may be an amide linking group. L¹ may be an amide linking group. L² may be an amide linking group.

Examples of amide linking groups include —C(O)NH— groups.

At least one of L¹ or L² may be an ester linking group. L¹ may be an ester linking group. L² may be an ester linking group.

Examples of ester linking groups include, but are not limited to, esters formed through the reactions between alcohols and aliphatic or aromatic di-acid or diacid chloride containing compounds.

At least one of L¹ or L² may be a phosphonate linking group. L¹ may be a phosphonate linking group. L² may be a phosphonate linking group.

L¹ or L² may be independently a linking group of Formula H:

wherein:

-   -   each of R^(d), and R^(f) is each independently selected from: an         optionally substituted straight chain, branched or cyclic,         saturated or unsaturated hydrocarbon radical (including         optionally substituted alkyl, alkenyl, alkynyl, aryl or         heterocyclyl radicals); and     -   R^(e) is selected from: hydrogen; or an optionally substituted         straight chain, branched or cyclic, saturated or unsaturated         hydrocarbon radical (including optionally substituted alkyl,         alkenyl, alkynyl, aryl or heterocyclyl radicals). For example,         substituent R^(e) may be an optionally substituted methyl group.

In one embodiment substituents L¹ and L² are the same. In another embodiment substituents L¹ and L² are different.

Substituents R¹, R², R³, R⁴, R⁵. R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ and R¹²

Herein, R¹, R², R³, R⁴, R⁷, R⁸, R⁹, and R¹⁰ are each independently selected from hydrogen and an optionally substituted straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical.

Herein, R⁵, R⁶, R¹¹ and R¹² are each independently selected from an optionally substituted straight chain, branched or cyclic, saturated and unsaturated hydrocarbon radical optionally interrupted with one or more heteroatoms independently selected from O, N and S.

In one embodiment at least one of R¹, R², R³, and R⁴ is an optionally substituted alkyl group. For example at least one of R¹, R², R³, and R⁴ is a methyl group.

In one embodiment each of R¹, R², R³, and R⁴ is an optionally substituted alkyl group. For example each of R¹, R², R³, and R⁴ is a methyl group.

In one embodiment at least two of R¹, R², R³, and R⁴ are the same substituent.

In one embodiment all of R¹, R², R³, and R⁴ are the same substituent.

In another embodiment at least one of R⁵ and R⁶ is independently selected from optionally substituted: propylene, butylene, pentylene, hexylene, ethoxypropyl, propoxypropyl and butoxypropyl groups.

In another embodiment both of R⁵ and R⁶ are selected from optionally substituted: propylene, butylene, pentylene, hexylene, ethoxypropyl, propoxypropyl and butoxypropyl groups.

In another embodiment at least one of R⁵ and R⁶ is independently selected from the moiety of Formula D:

wherein c is an integer between 1 and 6; and d is an integer between 1 and 6. For example c is 2 and/or d is 3.

In one embodiment R⁵ and R⁶ are the same substituent.

In one embodiment R⁵ and R⁶ are different substituents.

In one embodiment at least one of R⁷, R⁸, R⁹, and R¹⁰ is an optionally substituted alkyl group. For example at least one of R⁷, R⁸, R⁹, and R¹⁰ is a methyl group.

In one embodiment each of R⁷, R⁸, R⁹, and R¹⁰ is an optionally substituted alkyl group.

For example each of R⁷, R⁸, R⁹, and R¹⁰ is a methyl group.

In one embodiment at least two of R⁷, R⁸, R⁹, and R¹⁰ are the same substituent.

In one embodiment all of R⁷, R⁸, R⁹, and R¹⁰ are the same substituent.

In another embodiment at least one of R¹¹ and R¹² is independently selected from optionally substituted: propylene, butylene, pentylene, hexylene, ethoxypropyl, propoxypropyl and butoxypropyl groups.

In another embodiment both of R¹¹ and R¹² are selected from optionally substituted: propylene, butylene, pentylene, hexylene, ethoxypropyl, propoxypropyl and butoxypropyl groups.

In one embodiment, at least one of R¹¹ and R¹² is independently selected from the moiety

wherein a is an integer between 1 and 6; and b is an integer between 1 and 6. For example a is 2 and/or b is 3.

In one embodiment R¹¹ and R¹² are the same substituent. In another embodiment R¹¹ and R¹² are different substituents.

Substituents X and X¹

Herein, substituent X and X¹ may be independently selected from OC(O)O, C(O)O and O.

X may be OC(O)O. X may be C(O)O. X may be O. X¹ may be OC(O)O. X¹ may be C(O)O. X¹ may be O. X and X¹ may be the same. X and X¹ may be different.

Integers a, b, m, m′, m″, n, q, q, q″, r, r′, r″, t, u and v

Integer a may be: 1 or 2 or 3 or 4 or 5 or 6. In one embodiment, integer a is 2. In another embodiment, integer a is 3.

Integer b may be: 1 or 2 or 3 or 4 or 5 or 6. In one embodiment, integer b is 2. In another embodiment integer b is 3.

Herein integer m may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer m′ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer m″ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer n may be: 1 or 2 or 3 or 4 or 5.

Herein integer t may be: 0 or 1 or 2 or 3 or 4 or 5.

In one embodiment integer t is 0.

Herein integer q may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

In one embodiment integer q is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer q′ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

In one embodiment integer q′ is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer q″ may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

In one embodiment integer q″ is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer r may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer r′ may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer r″ may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer u may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

Herein integer v may be: 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

In one embodiment integer v is 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20.

Herein integer w may be: 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 10 or 11 or 12 or 13 or 14 or 15 or 16 or 17 or 18 or 19 or 20 or 21 or 22 or 23 or 24 or 25 or 26 or 27 or 28 or 29 or 30 or 31 or 32 or 33 or 34 or 35 or 36 or 37 or 38 or 39 or 40 or 41 or 42 or 43 or 44 or 45 or 46 or 47 or 48 or 49 or 50.

It will be appreciated that the above integer embodiments includes any integer range thereof. For example, a range may be provided between any two integers selected from each of the above described integer embodiments of a, b, m, n, q, r, t, u, v and w.

The block copolymer segment of Formula 1 according to any of the above described embodiments may have a molecular weight range between about 400 and 6000, or about 400 and 4000, or about 800 and 1600. Unless stated otherwise, herein the phrase “molecular weight” refers to the number-average molecular weight (M_(n)) of a particular polymer.

Thermoplastic Polyurethane or Polyurethaneurea Elastomer Compositions

Disclosed herein is a thermoplastic polyurethane or polyurethaneurea elastomer composition comprising a plurality of soft segments and hard segments, wherein the plurality of soft segments are each derived from at least one block copolymer segment of Formula 1 as defined herein and optionally an additional polyol or polyamine.

A thermoplastic polyurethane or polyurethaneurea elastomer composition may be provided comprising a plurality of soft segments and hard segments, wherein the plurality of soft segments are each derived from a single type of block copolymer segment selected from a block copolymer segment of Formula 1 as defined herein and optionally an additional polyol or polyamine.

Also disclosed herein is a thermoplastic polyurethane or polyurethaneurea elastomer composition comprising a plurality of soft segments and hard segments, wherein the plurality of soft segments are each derived from a mixture of two separate block copolymer segments of Formula 1 as defined herein and optionally an additional polyol or polyamine.

Also disclosed herein are thermoplastic polyurethane or polyurethaneurea elastomer compositions comprising a reaction product of:

-   -   i. at least one block copolymer segment of Formula 1 as defined         herein;     -   ii. a diisocyanate;     -   iii. one or more chain extenders; and     -   iv. optionally an additional polyol or polyamine.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomer composition may have a tensile strength of ≥5 MPa. For example the thermoplastic polyurethane or polyurethaneurea elastomer composition may have a tensile strength of: ≥7.5 MPa, or ≥10 MPa, or ≥12.5 MPa, or ≥15 MPa, or ≥17.5 MPa, or ≥20 MPa, or ≥22.5 MPa, or ≥25 MPa, or ≥27.5 MPa, or ≥30 MPa, or ≥32.5 MPa, or ≥35 MPa, or ≥37.5 MPa, or ≥40 MPa, or ≥42.5 MPa, or ≥45 MPa, or ≥47.5 MPa, or ≥50 MPa.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomer composition may have a Young's Modulus of ≥10 MPa. For example the thermoplastic polyurethane or polyurethaneurea elastomer composition may have a Young's Modulus of: ≥12.5 MPa, or ≥15 MPa, or ≥17.5 MPa, or ≥20 MPa, or ≥22.5 MPa, or ≥25 MPa, or ≥27.5 MPa, or ≥30 MPa, or ≥32.5 MPa, or ≥35 MPa, or ≥37.5 MPa, or ≥40 MPa, or ≥42.5 MPa, or ≥45 MPa, or ≥47.5 MPa, or ≥50 MPa, or ≥52.5 MPa, or ≥55 MPa, or ≥57.5 MPa, or ≥60 MPa, or ≥62.5 MPa, or ≥65 MPa, or ≥67.5 MPa, or ≥70 MPa, or ≥72.5 MPa, or ≥75 MPa, or ≥77.5 MPa, or ≥80 MPa.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomer composition may have an elongation at break of ≥500%. For example the thermoplastic polyurethane or polyurethaneurea elastomer composition may have an elongation at break of: ≥550%, or ≥600%, or ≥650%, or ≥700%, or ≥750%, or ≥800%, or ≥850%, or ≥900%, or ≥950%, or ≥1000%, or ≥1050%, or ≥1100%, or ≥1150%, or ≥1200%, or ≥1250%, or ≥1300%, or ≥1350%, or ≥1400%, or ≥1450%, or ≥1500%, or ≥1550%, or ≥1600%, or ≥1650%, or ≥1700%, or ≥1750%, or ≥1800%, or ≥1850%, or ≥1900%, or ≥1950%, or ≥2000%.

It will be appreciated that these tensile strengths may be measured using standard industry methods, for example a method adopted from ASTM Standard Method for thin Plastic Sheeting (e.g. ASTM D 882-02). In a further example, the method may involve thin films, for example about 200 to 300 microns, using the ASTM D 882-02 test method.

Example conditions which may be used to measure the tensile strength of a sample with ASTM D 882-02 method are:

-   -   using dumbbell shaped specimens which are 75 mm in length, 13 mm         in width at each end and 4 mm at the central narrow section         (with a constant width over at least 15 mm of length); and     -   using an Instron 5565 fitted with static load cell ±100 N and         calibrated using Instron Bluehill 2 (version 2.35) software.

For the tensile test with dry conditions, the specimen may be:

-   -   fixed between upper and lower grips (for example Instron grips)         such that the gap between the grips is 10 mm;     -   stretching the 10 mm long section of film at a rate of 50 mm per         minute until the film breaks;     -   performing at least three replicates, for example three, four or         five replicates.

For the tensile test with wet conditions, or replicating the conditions found for medical applications, the specimen may be:

-   -   placed in a plastic bag and immersed in water maintained at         37° C. for at least two hours;     -   dried using tissue paper and fixed between upper and lower grips         (for example Instron grips) such that the gap between the grips         is 10 mm;     -   stretched at a rate of 100 mm per min until the film breaks.

Stress, strain, breaking stress and elongation at breaking can be obtained using either the dry or wet conditions from the Instron Bluehill 2 (version 2.35) software. These parameters allow one to obtain values for the tensile strength, the Young's modulus (stiffness) and Elongation (elasticity) for a sample.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomer composition may have a polydispersity index (PDI) of ≤3.00. For example the thermoplastic polyurethane or polyurethaneurea elastomer composition may have a polydispersity index (PDI) of: ≤2.90, or ≤2.80, or ≤2.70, or ≤2.60, or ≤2.50, or ≤2.40, or ≤2.30, or ≤2.20, or ≤2.10, or ≤2.00, or ≤1.90, or ≤1.80, or ≤1.70, or ≤1.60, or ≤1.50, or ≤1.40, or ≤1.30, or ≤1.20, or ≤1.10.

In one embodiment a single block copolymer segment of Formula 1 is used in the formulation of the thermoplastic polyurethane or polyurethaneurea elastomer composition.

In another embodiment two different block copolymer segments of Formula 1 are used in the formulation of the thermoplastic polyurethane or polyurethaneurea elastomer composition.

Examples of mixtures one or two different block copolymer segments of Formula 1 or a combination of a block copolymer of Formula 1 and a macrodiol, which are used in the formulation of a thermoplastic polyurethane or polyurethaneurea elastomer composition, are shown in Table 1. Here Segment 1 and/or Segment 2 can be added in a reaction mixture with one or more chain extenders, a diisocyanate, to produce a thermoplastic polyurethane or polyurethaneurea elastomer composition. In these examples R^(5a) and R^(6a) may both be (CH₂)₂O(CH₂)₄.

TABLE 1 Examples of one or two different block copolymer segments of Formula 1, or a combination of a block copolymer of Formula 1 and a macrodiol, which are used in the formulation of a thermoplastic polyurethane or polyurethaneurea elastomer composition. In the following examples, R^(5a), R^(6a), m′ and r are as defined herein. Segment Number for Block Specific Segment Group Copolymer for Block Copolymer 1 Segment 1

Segment 2 — 2 Segment 1

Segment 2 — 3 Segment 1

Segment 2 — 4 Segment 1

Segment 2 — 5 Segment 1

Segment 2

6 Segment 1

Segment 2

7 Segment 1

Segment 2

8 Segment 1

Segment 2

Diisocyanates

Examples of appropriate diisocyanates include aliphatic, cyclic or aromatic diisocyanates such as, for example: 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, 1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI) trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) or its isomers (for example 2,6-toluene diisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylene diisocyanate (m-TMXDI), or 1,5-diisocyanatonaphthalene (NDI).

In one embodiment, the diisocyanate is MDI.

Chain Extender

Herein at least one chain extender is included in the formation of the thermoplastic polyurethane or polyurethaneurea elastomer compositions. A chain extender is a compound that has two functional groups per molecule, such as diols or diamines, which are capable of reacting with an isocyanate group.

The chain extender may have a molecular weight range of 400 or less. The chain extender may have a molecular weight range of about 800 to about 1600. The chain extender may have a molecular weight range of about 400 to about 4000.

The chain extender may be selected from diol or diamine chain extenders. In one embodiment at least one chain extender is a diol.

Examples of diol chain extenders include, but are not limited to: C₁₋₁₂alkane diols such as: 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-decanediol, 1,4-cyclohexane dimethanol, p-xyleneglycol, 1,4-bis (2-hydroxyethoxy) benzene, 1,12-dodecanediol and 1,3 bis-(4-hydroxybutyl) 1,1,3,3-tetramethyldisiloxane.

In one embodiment at least one chain extender is a diamine. Suitable diamine chain extenders include C₁₋₁₂ alkane diamines such as 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3 bis-(3-aminopropyl) tetramethyldisiloxane, or 1,3 bis-(3-aminobutyl) tetramethyldisiloxane.

The wt % of a hard segment in a thermoplastic polyurethane or polyurethaneurea (the wt % determined by the weight of a linking compound (for example a diisocyanate)+chain extender as a percentage of the total weight of the polyurethane/polyurethaneurea) may be in a range of about 20 wt % to about 60 wt %. Exemplified ranges include: about 30 wt % to about 60 wt %, or about 40 wt % to about 60 wt %, about 50 wt % to about 60 wt % and about 40 wt % to about 50 wt %.

In one embodiment only one chain extender is used in the formation of the thermoplastic polyurethane or polyurethaneurea elastomer composition.

In one embodiment two chain extenders are used in the formation of the thermoplastic polyurethane or polyurethaneurea elastomer composition. For example a combination of 1,4-butanediol and ethylene diamine.

Additional Polyol or Polyamine

Herein a thermoplastic polyurethane or polyurethaneurea elastomer compositions comprising a reaction product of: at least one block copolymer segment of Formula 1 as defined herein; a diisocyanate; and one or more chain extenders, may include an additional polyol or polyamine.

The additional polyols may include poly(hexamethylene oxide), poly(heptamethylene oxide), poly(octamethylene oxide) (POMO), poly(decamethylene oxide) (PDMO), polydimethylsiloxane diols, poly(butadine diol), poly(carbonate) diol and poly(isobutylene)diol.

In one embodiment the additional polyol may be: a polydimethylsiloxane polymer comprising at least two hydroxyl groups, for example α,ω bis-(6-hydroxyethoxypropyl)polydimethylsiloxane.

In one embodiment the additional polyol is a polyol of Formula J:

wherein:

-   -   R^(5a) and R^(6a) are each independently selected from a         straight chain, branched or cyclic, saturated and unsaturated         hydrocarbon radical optionally interrupted with one or more         heteroatoms independently selected from O, N and S; and     -   m′ is an integer of 1 to 50.

R^(5a) and R^(6a) may both be (CH₂)₂O(CH₂)₄.

In a another embodiment the additional polyol is a polyol of Formula K:

wherein:

X² is a group selected from: OC(O)O, C(O)O and O;

q′ is an integer of 1 to 50, including, for example, an integer of 5 to 20; and

r′ is an integer of 1 to 50.

In one embodiment X² is O.

In a another embodiment the additional polyol is selected from: poly(hexamethylene oxide), poly(heptamethylene oxide), poly(octamethylene oxide) (POMO) and poly(decamethylene oxide) (PDMO).

The additional polyamines may include α,ω bis-(3-aminopropyl)polydimethylsiloxane, α,ω bis-(aminomethyl)polydimethylsiloxane, a, bis-(2-aminoethyl)polydimethylsiloxane, α,ω bis-(4-aminobutyl)polydimethylsiloxane, α,ω bis-(5-aminopentyl)polydimethylsiloxane and the like.

The additional polyamine may be a polyamine of Formula L:

wherein:

-   -   R^(5b) and R^(6b) are each independently selected from a         straight chain, branched or cyclic, saturated and unsaturated         hydrocarbon radical optionally interrupted with one or more         heteroatoms independently selected from O, N and S; and     -   m″ is an integer of 1 to 50.

R^(5b) and R^(6b) may both be (CH₂)₂O(CH₂)₄.

The additional polyamine may be a polyamine of Formula M:

wherein:

X³ is a group selected from: OC(O)O, C(O)O and O;

q″ is an integer of 1 to 50, including, for example, an integer of 5 to 20; and

r″ is an integer of 1 to 50.

Processes for Preparing “Soft” Block Copolymers and Polyurethane or Polyurethaneurea Elastomer Compositions

Disclosed herein is a process for preparing a block copolymer segment of Formula 1, whereby the process comprising the step of combining:

-   -   i. at least one macrodiol; or     -   ii. at least one macrodiamine; or     -   iii. a mixture of at least one macrodiol and at least one         macrodiamine, with a divalent linking compound.

Optional additional steps may include one or more of:

-   -   i. filtration;     -   ii. the removal of solvent(s), for example via evaporation under         reduced pressure; and/or     -   iii. purification, for example by distillation (such as         distillation via the use of Kugelrohr distillation apparatus).

Herein divalent linking compounds are compounds that can link two components, such as two macrodiols or two macrodiamines, whereby the divalent compound is at the nexus between the two components. A divalent linking compound can create: urethane, urea, carbonate, amide, ester, and phosphonate linkages within the block copolymer segment.

Examples of divalent linking compounds are organophosphorus compounds or compounds comprising two functional groups, such as two: isocyanate, carboxylic acid and acid halide functional groups.

In one embodiment the divalent linking compound is a diisocyanate, for example: 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, 1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI) trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI) or its isomers (for example 2,6-toluene diisocyanate (2,6-TDI)), or mixtures thereof, p-tetramethylxylene diisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylene diisocyanate (m-TMXDI), or 1,5-diisocyanatonaphthalene (NDI).

In another embodiment the divalent linking compound is an acid halide, for example phosgene.

In another embodiment the divalent compound is an organophosphorus compound, for example methylphosphonic dichloride.

Also disclosed herein is a process for preparing a thermoplastic polyurethane or polyurethaneurea elastomer comprising the silicon based block copolymer segment of Formula 1, whereby the process comprises the steps of:

-   -   i. providing a block copolymer segment of Formula 1 or preparing         a block copolymer segment of Formula 1 using a process as         described herein;     -   ii. optionally further reacting the composition of step i. with         a divalent compound and: at least one macrodiol; at least one         macrodiamine; or a mixture of at least one macrodiol and at         least one macrodiamine; and     -   iii. reacting the block copolymer segment of step i. or ii. with         a chain extender or a mixture of chain extenders to form the         polyurethane or polyurethaneurea elastomer.

Non-limiting examples of soft segments which could be produced for the thermoplastic polyurethane or polyurethaneurea elastomeric compositions disclosed herein are shown in Schemes 1 to 4. In these schemes R^(5a) and R^(6a) are both (CH₂)₂O(CH₂)₄:

-   -   Scheme 1—The preparation of a linked macrodiol from         poly(hexamethylene oxide) (PHMO) using 4,4′-methylenediphenyl         diisocyanate (MDI) as the linker molecule.     -   Scheme 2—The preparation of a linked macrodiol from α,ω         bis-(6-hydroxyethoxypropyl)polydimethylsiloxane using MDI as the         linker molecule.     -   Scheme 3—The preparation of a linked macrodiol from         α,ω-bis-(6-hydroxyethoxypropyl)polydimethylsiloxane using a         carbonate linker:     -   Scheme 4—The preparation of a linked macrodiol from         α,ω-bis-(6-hydroxyethoxypropyl)polydimethylsiloxane using a         phosphonate linker.

As a non-limiting example, Scheme 5 illustrates a possible reaction scheme and the general structure of the polyurethane urea prepared from MDI linked PHMO and PDMS chain extended with ethylene diamine.

Materials, Devices and Articles

Disclosed herein are materials that comprise a thermoplastic polyurethane or polyurethaneurea elastomer composition as defined herein.

The thermoplastic polyurethane or polyurethaneurea elastomer compositions may be used to produce sheets of fabrics or fibres, especially for applications where materials possessing high tensile strength and/or tear strength are required. For example the thermoplastic polyurethane or polyurethaneurea elastomer compositions can be used to produce fibres that may be used in knitting or weaving specialty fabrics, for example high strength and/or water-repellent membranes. In addition, the thermoplastic polyurethane or polyurethaneurea elastomer compositions may be used as sealants. For compositions comprising a siloxane component, due to the dielectric properties of said siloxane component, the thermoplastic polyurethane or polyurethaneurea elastomer compositions may be used for electronic and electrical components and insulation.

Also disclosed herein are devices or articles which are composed wholly or partly of a thermoplastic polyurethane or polyurethaneurea elastomer composition as defined herein.

Examples of devices or articles include: artificial leather, shoe soles, cable sheathing, varnishes, coatings, structural components for pumps or vehicles, mining ore screens, conveyor belts, laminating compounds, fibres, textiles, separation membranes, sealants, and adhesive components.

Medical Devices, Articles or Implants

The thermoplastic polyurethane or polyurethaneurea elastomeric compositions defined herein may be used as biomaterials. Herein, the term “biomaterial” is used in its broadest sense and refers to a material which is used in situations where it comes into contact with the cells and/or bodily fluids of living animals or humans.

Disclosed herein are medical devices, articles or implants which are composed wholly or partly of a thermoplastic polyurethane or polyurethaneurea elastomeric composition as defined herein.

Examples of medical devices, articles and implants include: a cardiac pacemaker, defibrillator, catheter, heart valve, cardiac assist device, vascular graft, implantable prosthesis, a cannula, extra-corporeal device, artificial organ, pacemaker lead, defibrillator lead, blood pump, balloon pump, A-V shunt, biosensor, membrane for cell encapsulation, drug delivery device, wound dressing, artificial joint, orthopaedic implant, or soft tissue replacement.

In one embodiment the medical device, article or implant is for cardiovascular applications, for example a device, article or implant that relates to one or more of the aortic, mitral, pulmonary, and/or tricuspid valves.

In another embodiment the device may be a heart valve, or similar that can be inserted by a procedure called TAVI (Transcatheter Aortic Valve Replacement).

An example of an implantable valve 100 (for surgical and/or TAVI placement) is presented in FIG. 1. The valve includes a plurality of valve leaflets 110-1, 110-2, and 110-3 constructed from the subject polymers. Each of leaflets 110 can be discrete from the others (as shown) or can be portions of one unitary (monolithic) leaflet body. Support structure for the valve may include an annular base portion 102 that can have a planar or flat upstream terminus or can have a curved or scalloped upstream terminus (not shown) or extensions 104 that project from annular base portion 102 downstream relative to intended flow. The leaflets can be integrally formed on this base frame 102, such as through a casting (for example dip casting) or moulding process. In an example of a dip casting process, the base frame 102 is placed on a mandrel and dipped in a polymer, which results in the formation of leaflets integrated with a polymeric coating over the base frame. In some embodiments, leaflets 110 (formed of the subject polymers) can be physically joined to support structure 102 through a coupling process such as sewing.

Herein, the thermoplastic polyurethane or polyurethaneurea elastomeric compositions used in the production of a medical device, article or implant should be acceptable for use on or in a recipient, such as a human being. For example, the thermoplastic polyurethane or polyurethaneurea elastomeric composition, should be able to contact tissues of a recipient without excessive toxicity, irritation, allergic response or other potential complications commensurate with a reasonable benefit/risk ratio identified by a skilled medical professional or veterinarian.

It will be appreciated that in some cases thermoplastic polyurethane or polyurethaneurea elastomeric compositions as described herein may not be for use on or in a recipient, such as a human being, but can be useful in the preparation of thermoplastic polyurethane or polyurethaneurea elastomeric compositions which could be utilised in the preparation of materials which are acceptable for use in medical devices, articles and implants.

The recipients of medical devices, articles and implants described herein can be human beings, male or female.

Alternatively the recipients of medical devices, articles and implants described herein can be a non-human animal. “Non-human animals” or “non-human animal” is directed to the kingdom Animalia, excluding humans, and includes both vertebrates and invertebrates, male or female, and comprises: warm blooded animals, including mammals (comprising but not limited to primates, dogs, cats, cattle, pigs, sheep, goats, rats, guinea pigs, horses, or other bovine, ovine, equine, canine, feline, rodent or murine species), birds, insects, reptiles, fish and amphibians.

The recipients of the medical devices, articles and implants described herein are referred herein with the interchangeable terms “patient”, “recipient” “individual”, and “subject”. These four terms are used interchangeably and refer to any human or non-human animal (unless indicated otherwise), as defined herein.

EXAMPLES

Raw Materials

Certain chemicals referred to within the specification, including the following examples, can be obtained from the suppliers indicted in Table 2.

TABLE 2 Suppliers for selected compounds disclosed in the examples. Component Example Supplier α,ω Bis-(6- Shin-Etsu hydroxyethoxypropyl)polydimethylsiloxane (molecular weight 928) Hydrogenated poly(butadiene) diol Kraysol ® from Cray Valley 4,4′-methylene diphenyl diisocyanate BASF 1,4-Butanediol Aldrich 1,3 bis-(3-aminopropyl) Shin-Etsu tetramethyldisiloxane 1,1,3,3-Bis-hydroxybutyl tetramethyl Shin-Etsu disiloxane Equipment

Gel Permeation Chromatography: Waters THF System

Gel permeation chromatography (GPC) was performed on a Waters Alliance system equipped with an Alliance 2695 Separations Module (integrated quaternary solvent delivery, solvent degasser and autosampler system), a Waters column heater module, a Waters 2414 RDI refractive index detector, a Waters PDA 2996 photodiode array detector (210 to 400 nm at 1.2 nm) and 4× Agilent PL-Gel columns (3×PL-Gel Mixed C (5 m) and 1×PL-Gel Mixed E (3 m) columns), each 300 mm×7.8 mm², providing an effective molar mass range of 10 to 4×10⁵). Tetrahydrofuran (THF) high purity solvent (HPLC grade) was pre-filtered through aluminium oxide (90 active neutral, 70-230 mesh) with 0.45 m filter, and 0.1 g L¹ 2,6-di-tert-butyl-4-methylphenol (BHT) was added as inhibitor. The filtered THF containing BHT was purged slowly with nitrogen gas and used as an eluent with a flow rate of 1 mL/min at 30° C. Number (M_(n)) and weight average (M_(w)) molar masses were evaluated using Waters Empower-3 software. The GPC columns were calibrated with low dispersity polystyrene (PSt) standards (Polymer Laboratories) ranging from 265 to 2,560,000 g mol⁻¹, and molar masses are reported as PSt equivalents. A 3rd-order polynomial was used to fit the log M_(p) vs. time calibration curve, which was near linear across the molar mass ranges.

Gel Permeation Chromatography: Shimadzu—DMAc

Gel permeation chromatography (GPC) was performed on a Shimadzu system equipped with a CMB-20A controller system, an SIL-20A HT autosampler, an LC-20AT tandem pump system, a DGU-20A degasser unit, a CTO-20AC column oven, an RDI-10A refractive index detector, and 4× Waters Styragel columns (HT2, HT3, HT4, and HT5, each 300 mm×7.8 mm², providing an effective molar mass range of 100-4×10⁶). N,N-Dimethylacetamide (DMAc) (containing 4.34 g L⁻¹ lithium bromide (LiBr)) was used as an eluent with a flow rate of 1 mL/min at 80° C. Number (M_(n)) and weight average (M_(w)) molar masses were evaluated using Shimadzu LC Solution software. The GPC columns were calibrated with low dispersity polystyrene (PSt) standards (Polymer Laboratories) ranging from 575 to 3,242,000 g mol⁻¹, and molar masses are reported as PSt equivalents. A 3rd-order polynomial was used to fit the log M_(p) vs. time calibration curve, which was near linear across the molar mass ranges

Film Preparation by Solvent Casting and Testing of Mechanical Properties

Polymer films of 80 mm×145 mm size were prepared by placing a solution of the polymer in a Teflon mould and then evaporating the solvent slowly in a nitrogen circulating oven at 60° C. for few hours followed by further drying under a vacuum (1 torr) overnight. The films were then equilibrated at room temperature for at least 24 hours before using them for tensile property measurement.

Dumbbell shaped specimens of polymer film were punched using a die and a manual cutting Press (IDM Instruments). The specimens had dimensions of 75 mm length, 13 mm width at each end and 4 mm at the central narrow section (constant width over at least 15 mm of length). Thickness of the cut out specimen was measured using a digital thickness gauge (Mitutoyo, Japan). In case there was small variation in thickness over the length of 15 mm in the central narrow section, an average of three thickness values was taken. Instron 5565 fitted with static load cell ±100 N was initialized and the load was calibrated using Instron Bluehill 2 (version 2.35) software. For the tensile test at dry condition, the specimen was fixed between upper and lower grips (Instron) such that the gap between the grips was 10 mm. The 10 mm long section of the film was stretched at the rate of 50 mm per minute until the film broke. At least three replicates of specimen were tested for each film. In case of wide discrepancy between results, five tests were carried out. Stress, strain, breaking stress and elongation at breaking were obtained from the software. These parameters allow one to obtain values for the tensile strength, the Young's modulus (stiffness) and Elongation (elasticity) of the samples.

For the tensile test at wet condition, (or replication of conditions found in medical applications) the cut out specimen of known thickness was put in a plastic bag and immersed in water maintained at 37° C. for at least two hours. The specimen was quickly dried using tissue paper and fixed between the grips and stretched at the rate of 100 mm per min until the film broke. Stress, strain, breaking stress and elongation at breaking were obtained from the software. The stress values were plotted against strain (% of initial value).

Abbreviated Terms

Table 3 lists a series of abbreviated terms which are used herein.

TABLE 3 Acronyms used for compounds and components described herein Acronym Compound/Component BAPD 1,3 Bis-(3-aminopropyl) tetramethyldisiloxane DMAc N′N-Dimethylacetamide GPC Gel Permeation Chromatography MDI 4,4′-Methylenediphenyldiisocyanate M_(n) Number Average Molecular Weight M_(w) Weight Average Molecular Weight PDI Polydispersity Index PDMS α,ω Bis-(6-hydroxyethoxypropyl)polydimethylsiloxane PHMO Poly(hexamethylene oxide) PU Polyurethane PUU Polyurethaneurea EDA 1,2-ethanediamine BDO 1,4-butanediol BHTD 1,1,3,3-bis-hydroxybutyltetramethylene disiloxane

Example 1—Synthesis of Urethane Linked Poly(Hexamethylene Oxide) (PHMO-u-PHMO)

Poly(hexamethylene oxide) (PHMO) (molecular weight 696.23) was prepared according to a method described in:

-   -   P. A. Gunatillake, G. F. Meijs, R. C. Chatellier, D. M. McIntosh         and E. Rizzardo, Polym. Int., 7, 275-283, 1992; and     -   U.S. Pat. No. 5,403,912.         The PHMO was dried and degassed by heating at 105° C. for about         15 hours under vacuum (0.1 torr) until the moisture content was         below 200 ppm, as determined by Karl Fisher titration. All         glassware used were dried overnight at 105° C. prior to use in         the experiment. Accurately weighed molten         4,4′-methylenediphenyldiisocyanate (MDI) (7.18 g) was placed in         a round bottom flask equipped with: a mechanical stirrer,         addition funnel and a nitrogen inlet. The flask was then placed         in an oil batch at 80° C. Pre-dried PHMO (40.00 g) was weighed         and added to MDI with stirring over a period of 20 minutes. The         reaction mixture was further reacted for about 2 hours until all         the isocyanate was consumed. This was confirmed by the absence         of an IR absorption band at 2275 cm¹.

Characterisation data for the PHMO prior to and after linking is shown in

Table 4.

TABLE 4 Molecular Weight Characterisation Data for Example 1: System M_(n) M_(w) PDI PHMO - Before Linking 1333 1999 1.49 PHMO - After Linking 4322 7272 1.68 (Urethane)

The linked-PHMO was stored under nitrogen at ambient temperature until further use.

Example 2—Synthesis of Urethane Linked α,ω Bis-(6-hydroxyethoxypropyl)-polydimethylsiloxane (PDMS-u-PDMS)

α,ω Bis-(6-hydroxyethoxypropyl)polydimethylsiloxane (molecular weight 928) was dried and degassed at 105° C. for about 15 hours until the moisture content was below 200 ppm as determined by Karl Fisher titration. All glassware used were dried overnight at 105° C. before use in the experiment. Accurately weighed molten MDI (6.74 g) was placed in a round bottom flask equipped with: a mechanical stirrer, addition funnel and a nitrogen inlet. The flask was then placed in an oil batch at 80° C. Pre-dried PDMS (50.0 g) was weighed accurately and added to MDI with stirring over a period of 20 minutes. The reaction mixture was further reacted with stirring at 80° C. for about 2 hours until all the isocyanate was consumed, which was confirmed by the absence of an IR absorption band at 2275 cm¹.

Characterisation data for the PHMO prior to and after linking is shown in

Table 5.

TABLE 5 Molecular Weight Characterisation Data for Example 2: PDI System M_(n) M_(w) (=M_(w)/M_(n)) Siloxane - Before 1334 1475 1.30 Linking Siloxane - After 5302 7468 1.40 Linking (Urethane)

The results showed that the linking reaction was successful. Following the reactions, the product was stored under nitrogen at ambient temperature.

Example 3—Synthesis of the Carbonate Linked PDMS (PDMS-c-PDMS)

In a three-necked 1 L round bottomed flask equipped with: a silica gel drying tube, a 250 mL pressure compensating dropping funnel, a thermometer, and a magnetic stirrer bar, were placed 200 ml of dry toluene and 49.48 g of a 20% solution of phosgene in toluene. The flask was cooled, whilst stirring, to 0° C. 23.62 g of pyridine was added dropwise to the mixture from the dropping funnel. The addition was made over a 15 minute period during which time the temperature was maintained in the range 0-5° C. 270.82 g of α,ω-bis(hydroxyethoxypropyl) polydimethylsiloxane (molecular weight 928) was then added drop wise to the mixture from the dropping funnel. The addition was made over a 1 hour period during which time the temperature of the mixture rose to 15° C. after which the reaction mixture was maintained at 15° C. for 2 hours. During this period pyridine hydrochloride precipitated out of the reaction mixture. The reaction mixture was filtered through celite to remove the pyridine hydrochloride. The toluene was removed by rotary evaporator at 80° C. under a reduced pressure of 20 torr. The mixture was transferred to a Kugelrohr distillation apparatus and stripped of low molecular weight species at 150° C. under a reduced of 8×10⁻² torr to give 202 g of (PDMS-1000)-c-(PDMS-1000) as a colourless oil (molecular weight 1924).

Example 4—Synthesis of the Phosphate Linked PDMS (PDMS-p-PDMS)

In a 500 ml round bottomed flask equipped with a magnetic stirrer bar were placed 100 ml of dry ether, 69.82 g of α,ω-bis(hydroxyethoxypropyl) polydimethylsiloxane (molecular weight 928), and 7.61 g of triethylamine. A solution of 23.62 g of methylphosphonic dichloride in 50 ml of ether was added drop wise to the mixture from the dropping funnel. During this period triethylamine hydrochloride precipitated out of the reaction mixture. The reaction was stirred for a further 3 days at room temperature. The reaction mixture was filtered to remove the pyridine hydrochloride. The ether was removed by rotary evaporator at 80° C. under a reduced pressure of 20 torr to give 72 g of PDMS-1000-P(O)Me-PDMS as a colourless oil.

Example 5—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BAPD with 40 Hard Segment Percentage

Accurately weighed linked PHMO-u-PHMO (10.00 g) prepared according to the method described in Example 1, and α,ω-bis(hydroxyethoxypropyl) polydimethylsiloxane (PDMS) (MW 973, 40.00 g) were mixed in a flask and degassed at 80° C. under vacuum (0.1 torr) for 2 hours. MDI (22.94 g) was accurately weighed in to a round bottom flask equipped with: a mechanical stirrer, addition funnel and a nitrogen inlet. The flask was then placed in an oil batch at 80° C. The mixture of PHMO-u-PHMO and PDMS was added slowly over period of 30 minutes using an addition funnel to with stirring to MDI in the flask. After the addition was over, the reaction mixture was heated at 80° C. for 2 hours with stirring under nitrogen. Anhydrous N′N-dimethylacetamide (DMAc, 500 mL) was then added using a syringe to the reaction mixture and stirred for 5 minutes until a clear solution is obtained. The solution was cooled in an ice bath to 0° C. and 1,3 bis-(3-aminopropyl) tetramethyldisiloxane (BAPD, 10.40 g) dissolved in anhydrous DMAc (25 mL) was added dropwise to the pre-polymer solution in the flask with stirring. After the addition was over, the polymer solution was heated to 90° C. for a period of 3 hours and transferred into a Schott bottle.

The polymer solution, after allowing to degas, was cast as thin film by pouring on to a Teflon mould. The mould was placed in an oven under a slow stream of nitrogen at 60° C. for 6 hours to remove the solvent, followed by placing it under vacuum (0.1 torr) for a further 16 hours to remove any remaining solvent.

Characterisation data for the prepared polymer is shown in Table 6.

Example 6—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-u-PDMS, PHMO, BAPD with 40 Hard Segment Percentage

Accurately weighed linked PDMS-u-PDMS (40.00 g) prepared according to the method described in Example 2, and PHMO (MW 696, 10.00 g) were mixed in a flask and degassed at 80° C. under vacuum (0.1 torr) for 2 hours. MDI (21.19 g) was accurately weighed in to a round bottom flask equipped with: a mechanical stirrer, addition funnel and a nitrogen inlet. The flask was then placed in an oil batch at 80° C. The mixture of PDMS-u-PDMS and PHMO was added slowly over period of 30 minutes using an addition funnel to with stirring to MDI in the flask. After the addition was over, the reaction mixture was heated at 80° C. for 2 hours with stirring under nitrogen. Anhydrous DMAc (500 ml) was then added using a syringe to the reaction mixture and then stirred for 5 minutes until a clear solution was obtained. The solution was cooled in an ice bath to 0° C. and BAPD (12.14 g) dissolved in anhydrous DMAc (25 mL) was added dropwise to the pre-polymer solution in the flask with stirring. After the addition was over, the polymer solution was heated to 90° C. for a period of 3 hours and transferred into a Schott bottle.

The polymer solution, after allowing to degas, was cast as thin film by pouring on to Teflon mould. The mould was placed in an oven under a slow stream of nitrogen at 60° C. for 6 hours to remove the solvent, followed by placing the mould under vacuum (0.1 torr) for 16 hours to remove any remaining solvent.

Characterisation data for the prepared polymer is shown in Table 6.

Example 7—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-c-PDMS, PHMO, BAPD with 40 Hard Segment Percentage

Accurately weighed linked PDMS-c-PDMS (40.00 g) prepared according to the method described in Example 2, and PHMO (molecular weight 696, 10.00 g) were mixed in a flask and degassed at 80° C. under vacuum (0.1 torr) for 2 hours. MDI (21.42 g) was accurately weighed in to a round bottom flask equipped with: a mechanical stirrer, addition funnel and a nitrogen inlet. The flask was then placed in an oil batch at 80° C. The mixture of PDMS-c-PDMS and PHMO was added slowly over period of 30 minutes using an addition funnel to with stirring to MDI in the flask. After the addition was over, the reaction mixture was heated at 80° C. for 2 hours with stirring under nitrogen. Anhydrous DMAc (500 mL) was then added using a syringe to the reaction mixture and stirred for 5 minutes until a clear solution was obtained. The solution was cooled in an ice bath to 0° C. and BAPD (11.91 g) dissolved in anhydrous DMAc (25 mL) was added dropwise to the pre-polymer solution in the flask with stirring. After the addition was over, the polymer solution was heated to 90° C. for a period of 3 hours and transferred into a Schott bottle.

The polymer solution, after allowing to degas, was cast as thin film by pouring on to Teflon mould. The mould was placed in an oven under a slow stream of nitrogen at 60° C. for 6 hours to remove DMAc, followed by under vacuum (0.1 torr) for 16 hours to remove any remaining solvent.

Characterisation data for the prepared polymer is shown in Table 6.

Example 8—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-u-PDMS and BAPD without PHMO with 40 Hard Segment Percentage

Accurately weighed linked PDMS (40.0 g) was degassed at 80° C. for 2 hours under vacuum (0.1 torr). Molten MDI (15.88 g) was placed in a three necked flask equipped with: a mechanical stirrer, dropping funnel and a nitrogen inlet. The flask was then placed in an oil bath at 70° C. The degassed macrodiol mixture (50 g) was added dropwise through the addition funnel over a period of 30 minutes. After the addition was over, the reaction mixture was heated at 80° C. for 2 hours with stirring under nitrogen. Anhydrous DMAc (500 mL) was then added through a syringe to the reaction mixture and stirred for 5 minutes until it was a clear solution. The solution was then cooled in an ice bath to 0° C. and BAPD (10.79 g) mixed with anhydrous DMAc (50 mL) was added dropwise into the above solution. After the addition was over, the above polymer solution was heated to 90° C. for a period of 3 hours and transferred into a Schott bottle. The polymer solution was then degassed at 60° C. in a nitrogen circulating oven and cast into a 0.5-mm thick film.

The polymer solution, after allowing to degas, was cast as thin film by pouring on to Teflon mould. The mould was placed in an oven under a slow stream of nitrogen at 60° C. for 6 hours to remove solvent. The mould was then placed under vacuum (0.1 torr) for 16 hours to remove any remaining solvent.

Example 9—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-c-PDMSO, BDO with 40 Hard Segment Percentage by One-Step Bulk Polymerisation

A mixture of pre-dried linked PDMS-c-PDMS (20.0 g) and 1,4-butanediol (BDO) (2.85 g) was weighed in a PP beaker and degassed at 80° C. under a vacuum of 0.1 torr for over an hour. The vacuum was released under nitrogen and dibutyltindilaurate (DBTL) catalyst 0.1 wt-% was added and stirred manually with the spatula. Molten MDI (10.49 g) was then added to the reaction mixture at once and stirred rapidly using spatula until viscous enough and then poured into Teflon tray and cured at 100° C. for 18 hours. The polymer was then compression moulded into a film using hot press at 180° C. for mechanical properties.

Example 10—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BAPD with 50 Hard Segment Percentage

A PUU was synthesised according procedure as described in Example 5. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);     -   PDMS (40.0 g);     -   MDI (31.68 g); and     -   BAPD (18.32 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 11—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, EDA with 50 Hard Segment Percentage

The PUU was synthesised according procedure as described in Example 5. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);     -   PDMS (40.0 g);     -   MDI (42.94 g); and     -   EDA (7.06) g.

Characterisation data for the prepared PUU is shown in Table 6.

Example 12—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-u-PDMS, PHMO, BAPD with 50 Hard Segment Percentage

A PUU was synthesised according to the procedure as described in Example 5. The following quantities of reagents were used:

-   -   linked PDMS-u-PDMS (40.0 g);     -   PHMO (10.0 g);     -   MDI (29.39 g); and     -   BAPD (20.61 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 13—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BAPD:EDA (8:2) with 50 Hard Segment Percentage

A mixture of PDMS (40.0 g) and PHMO-u-PHMO (10.0 g) was degassed at 80° C. for 2 hours under vacuum (0.1 torr). Molten MDI (32.91 g) was placed in a three necked flask equipped with: a mechanical stirrer, dropping funnel and a nitrogen inlet. The flask was then placed in an oil bath at 70° C. The degassed macrodiol mixture (50 g) was added dropwise through the addition funnel over a period of 30 minutes. After the addition was over, the reaction mixture was heated at 80° C. for 2 hours with stirring under nitrogen. Anhydrous DMAc (500 mL) was then added through a syringe to the reaction mixture and stirred for 5 minutes until it was a clear solution. The solution was then cooled in an ice bath to 0° C. BAPD (16.11 g) mixed with ethylene diamine (0.97 g) dissolved in anhydrous DMAc (60 mL) was added dropwise into above solution. After the addition was over, the above polymer solution was heated to 90° C. for a period of 3 hours and transferred into a Schott bottle. The polymer solution was then degassed at 60° C. in a nitrogen circulating oven and cast into a thin film as described in Example 5.

Characterisation data for the prepared PUU is shown in Table 6.

Example 14—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BHTD:EDA (6:4) with 45 Hard Segment Percentage

A mixture of PDMS (40.0 g) and PHMO-u-PHMO (10.0 g) was degassed at 80° C. for 2 hours under vacuum (0.1 torr). Molten MDI (28.65 g) was placed in a three necked flask equipped with: a mechanical stirrer, dropping funnel and a nitrogen inlet. The flask was then placed in an oil bath at 70° C. The degassed macrodiol mixture (50.0 g) was added through the addition funnel over a period of 30 minutes. After the addition was over, the reaction mixture was heated at 80° C. for 2 hours with stirring under nitrogen. 1,1,3,3-Bis-hydroxybutyltetramethylene disiloxane (BHTD) (10.72 g) was then added to the reaction mixture and the system was allowed to react for a further 2 hours. The reaction mixture was then cooled down to 0° C. and anhydrous DMAc (500 mL) was then added through a syringe to the reaction mixture and stirred for 5 minutes until it was a clear solution. EDA (1.54 g) dissolved in anhydrous DMAc (60 mL) was added dropwise into above solution. After the addition was over, the above polymer solution was heated to 90° C. for a period of 3 hours and then transferred into a Schott bottle. The polymer solution was then degassed at 60° C. in a nitrogen circulating oven and cast into a thin film as described in Example 5.

Characterisation data for the prepared PUU is shown in Table 6.

Example 15—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BHTD:EDA (4:6) with 45 Hard Segment Percentage

The PUU was synthesised according to the procedure described in Example 14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);     -   PDMS (40.0 g);     -   MDI (30.42 g);     -   BHTD (7.93 g); and     -   EDA (2.57 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 16—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BDO:EDA (6:4) with 45 Hard Segment Percentage

The PUU was synthesised according to the procedure described in Example 14. The following quantities of reagents were used:

linked PHMO-u-PHMO (10.0 g);

-   -   PDMS (40.0 g);     -   MDI (34.19 g);     -   BHTD (4.65 g); and     -   BDO (2.07 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 17—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-u-PDMS, PHMO, BHTD:EDA (6:4) with 45 Hard Segment Percentage

The PUU was synthesised following procedure as described in Example 14. The amount of precursors used are as follows:

-   -   linked PHMO-u-PHMO (10.0 g);     -   PDMS (40.0 g);     -   MDI (26.92 g);     -   BHTD (12.23 g); and     -   EDA (1.76 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 18—Preparation of a Polyurethaneurea (PUU) Using Linked PDMS-u-PDMS, PHMO-u-PHMO, BHTD:EDA (6:4) with 45 Hard Segment Percentage

The PUU was synthesised according to the procedure described in Example 14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);     -   PDMS-u-PDMS (40.0 g);     -   MDI (26.02 g);     -   BHTD (13.02 g); and     -   EDA (1.87 g).

Characterisation data for the prepared PUU is shown in Table 6.

Example 19—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BHTD:EDA (50:50) with 45 Hard Segment Weight Percentage

The PUU was synthesised according to the procedure described in Example 14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (20.0 g);     -   PDMS (80.0 g);     -   MDI (58.33 g);     -   BHTD (19.32 g); and     -   EDA (4.17 g).

Example 20—Preparation of a Polyurethaneurea (PUU) Using Linked PHMO-u-PHMO, PDMS, BAPD with 40 Hard Segment Weight Percentage

The PUU was synthesised according to the procedure described in Example 14. The following quantities of reagents were used:

-   -   linked PHMO-u-PHMO (10.0 g);     -   PDMS (40.0 g);     -   MDI (29.32 g); and     -   BAPD (4.02 g)

Example 21—Tensile Testing of the Materials Produced in Examples 5-7, 10 & 12-20

Tensile testing was carried out using dumbbells punched from dried polyurethaneurea films prepared in Examples 5 to 7, 10 and 12-20. Tensile testing was carried out on an Instron model 5565 Universal Testing Machine. The results are summarised in Table 6. These results indicate that the polyurethaneurea polymers of the current invention demonstrate high tensile strength and high elongation compared to polyurethaneurea polymers in the prior art.

Tensile testing of films prepared in Examples 13, 17, 18 and 20 was carried out on an Instron model 5565 Universal Testing Machine using the procedure described under the heading “Equipment”.

Characterisation data for the prepared PUUs are shown in Table 6 and Table 7.

TABLE 6 The molecular weight and tensile properties of polyurethaneureas prepared as described in Examples 5-7, 10 and 12-20 -21measured at ambient temperature. Ultimate Tensile Young's Elongation Strength Modulus at Break GPC Characterisation Data Example (MPa) (MPa) (%) Mn Mw PDI 5 20.6 ± 2.5 11.20 ± 0.8  1871 ± 26 85762 192726 2.2 6 22.26 ± 1.7  16.6 ± 0.7 1361 ± 12 86486 208711 2.35 7  6.0 ± 0.8 20.7 ± 4.0  570 ± 20 69106 214173 2.8 10 14.98 ± 6.3  16.6 ± 0.7 1361 ± 12 72816 142744 1.94 12 20.6 ± 2.5 11.20 ± 0.8  1871 ± 26 85762 192726 2.2 13 28.47 ± 1.5  57.7 ± 2.6  830 ± 4.9 119896 351073 2.53 14 18.5 ± 3.2 21.6 ± 3.0 1170 ± 13 143469 544021 2.73 15 36.8 ± 0.8 52.8 ± 0.5 1100 ± 30 129302 272731 2.01 16 31.7 ± 0.3 66.2 ± 6.1  860 ± 84 82800 156265 1.83 17  26.6 ± 13.4 39.28 ± 8.5   990 ± 36 123109 394717 2.65 18 36.7 ± 3.6 35.1 ± 1.8 1180 ± 11 104911 213576 1.95 19 34.0 ± 2.7 35.8 ± 2.1 1367 ± 42 89147 253274 2.84 20 23.6 ± 2.4 67.97 ± 10.9  800 ± 12 87372 158008 1.73

TABLE 7 The tensile properties of polyurethaneureas prepared as described in Examples 13, 17, 18, and 20 measured at 37° C. temperature. Ultimate Tensile Young's Modulus Elongation at Example Strength (MPa) (MPa) Break (%) 13 27.53 ± 2.8 29.44 ± 0.63 950 ± 3 17  22.96 ± 10.64 37.09 ± 4.8   860 ± 25 18 30.55 ± 3.2 28.84 ± 0.59 1180 ± 11 20 23.06 ± 2.3 56.49 ± 4.2  880 ± 5

The polyurethaneureas prepared according to the present invention exhibit high tensile strength, low modulus and high elongation as shown in Table 6. In particular, the polyurethaneureas prepared according to Examples 15 and 16 had tensile strength exceeding 30 MPa with elongation at break over 1000%. This combination of properties is unique and far exceeded those reported in prior art. For example, the polyurethaneureas disclosed in International Patent Application WO00/64971 had elongations at break less than 500% for materials described in all Examples.

It will be appreciated by persons skilled in the art that numerous variations and/or modifications may be made to the above-described embodiments, without departing from the broad general scope of the present disclosure. For example, it will be appreciated that embodiments may be variously combined or separated without parting from the invention and that the preferred features described herein are applicable to all aspects of the invention described herein. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. 

What is claimed is:
 1. A polymer comprising a plurality of hard segments; a first plurality of soft segments comprising a linked macrodiol having a structure of Formula 1; and a second plurality of soft segments comprising a polyol,

wherein A¹ is a hydroxyl group; A² is hydrogen or a hydroxyl group; each Y¹ and Y² independently comprises a polysiloxane macrodiol, polyether macrodiol, polycarbonate macrodiol, polyester macrodiol, or a polyhydrocarbon macrodiol; each L¹ and L² is independently a first divalent linking group; the first divalent linking group is created from a first divalent linking compound; the first divalent linking compound is a diisocyanate; n is an integer of 1 to 5; t is 0 to 5; and Q is represented by Formula A or Formula B:

wherein R¹, R², R³, and R⁴, are each independently selected from hydrogen and an optionally substituted straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical; R⁵ and R⁶ are each independently selected from a straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical optionally interrupted with one or more heteroatoms independently selected from O, N and S; m is an integer of 1 to 50; X is a group selected from OC(O)O, C(O)O and O; q is an integer of 1 to 50; and r is an integer of 2 to 50, provided that (i) Q is represented by Formula B where X is 0, (ii) Y² is a polyether macrodiol, or (iii) the second plurality of soft segments comprises a polyether macrodiol.
 2. The polymer of claim 1, wherein Q is


3. The polymer of claim 1, wherein the first divalent linking compound is selected from 1,4-diisocyanatobutane, 1,12-diisocyanatododecane, 1,6-diisocyantehexane, 1,8-diisocyanateoctane, 4,4′-methylenediphenyl diisocyanate (MDI), 4,4′-methylenebis(cyclohexyl diisocyanate) (H12MDI), p-phenylene diisocyanate (p-PDI), m-phenylene diisocyanate (m-PDI), trans-cyclohexane-1,4-diisocyanate (CHDI) or a mixture of the cis and trans isomers, 1,6-hexamethylene diisocyanate (HDI), 2,4-toluene diisocyanate (2,4-TDI), 2,6-toluene diisocyanate (2,6-TDI), p-tetramethylxylene diisocyanate (p-TMXDI), isophorone diisocyanate or m-tetramethylxylene diisocyanate (m-TMXDI), 1,6-diisocyanatohexane (DICH), 1,3-bis(1-isocyanato-1-methylethyl)benzene, and 1,5-diisocyanatonaphthalene (NDI).
 4. The polymer of claim 1, wherein the first divalent linking compound is MDI.
 5. The polymer of claim 1, wherein Q is represented by Formula B; X is O; and q is
 6. 6. The polymer of claim 1, wherein t is 0; Q is represented by Formula B; the first divalent linking compound is MDI; Y² is a polyether macrodiol.
 7. The polymer of claim 1, wherein the linked macrodiol has a structure of Formula 1B(i)(a):

wherein X and X¹ are O; v is an integer of 1 to 50; and w is an integer of 2 to
 50. 8. The polymer of claim 1, wherein the linked macrodiol has the following structure:


9. The polymer of claim 1, wherein the polyol in the second plurality of soft segments has the following structure:

wherein R^(5a) and R^(6a) are each independently selected from a straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical optionally interrupted with one or more heteroatoms independently selected from O, N and S; and m′ is an integer of 1 to
 50. 10. The polymer of claim 1, wherein the linked macrodiol has the following structure:

and the polyol in the second plurality of soft segments has the following structure:

wherein R^(5a) and R^(6a) are each independently selected from a straight chain, branched or cyclic, saturated or unsaturated hydrocarbon radical optionally interrupted with one or more heteroatoms independently selected from O, N and S; and m′ is an integer of 1 to
 50. 11. The polymer of claim 1, wherein the plurality of hard segments comprise a chain extender covalently linked to soft segments via a second divalent linking group.
 12. The polymer of claim 11, wherein the first divalent linking group and the second divalent linking group are the same.
 13. The polymer of claim 11, wherein the chain extender is a C₁₋₁₂ alkane diol or a C₁₋₁₂ alkane diamine.
 14. The polymer of claim 11, wherein the chain extender is selected from 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexane dimethanol, p-xyleneglycol, 1,4-bis(2-hydroxyethoxy)benzene, 1,12-dodecanediol, 1,3-bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane, 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,3-bis-(3-aminopropyl)tetramethyldisiloxane, and 1,3-bis-(3-aminobutyl)-tetramethyldisiloxane.
 15. The polymer of claim 11, wherein the chain extender comprises 1,3 bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane.
 16. The polymer of claim 11, wherein the chain extender comprises 1,2-ethylenediamine.
 17. The polymer of claim 11, wherein the chain extender comprises 1,2-ethylenediamine and 1,3 bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane covalently linked by a third divalent linking group.
 18. The polymer of claim 17, wherein the third divalent linking group is created from a third divalent linking compound; and the third divalent linking compound is a diisocyanate.
 19. The polymer of claim 18, wherein the third divalent linking compound is MDI.
 20. The polymer of claim 1, wherein Y² and the polyol are not the same.
 21. The polymer of claim 1, wherein Y² is a polyether macrodiol.
 22. The polymer of claim 1, wherein the second plurality of soft segments comprises poly(hexamethylene oxide), poly(heptamethylene oxide), poly(octamethylene oxide), poly(decamethylene oxide), polydimethylsiloxane diols, poly(butadine diol), poly(carbonate) diol, poly(isobutylene)diol, or α,ω bis-(6-hydroxyethoxypropyl)polydimethyl-siloxane.
 23. The polymer of claim 1, wherein Y² is poly(hexamethylene oxide); and the second plurality of soft segments comprises poly(hexamethylene oxide), poly(heptamethylene oxide), poly(octamethylene oxide), poly(decamethylene oxide), polydimethylsiloxane diols, poly(butadine diol), poly(carbonate) diol, poly(isobutylene)diol, or α,ω bis-(6-hydroxyethoxypropyl)polydimethyl-siloxane.
 24. The polymer of claim 1, wherein t is 0; Q is poly(hexamethylene oxide); the first divalent linking compound is MDI; Y² is poly(hexamethylene oxide); the second plurality of soft segments comprises α,ω bis-(6-hydroxyethoxypropyl)polydimethyl-siloxane; the plurality of hard segments comprise a chain extender covalently linked to soft segments via a second divalent linking group; the second divalent linking group is created from a second divalent linking compound; the second divalent linking compound is MDI; the chain extender comprises 1,2-ethylenediamine and 1,3 bis-(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane covalently linked by a third divalent linking group; the third divalent linking group is created from a third divalent linking compound; and the third divalent linking compound is MDI.
 25. The polymer of claim 1, wherein the polymer is not crosslinked. 